Photocatalytic Methanol Dehydrogenation Promoted Synergistically by Atomically Dispersed Pd and Clustered Pd

Supported metal in the form of single atoms, clusters, and particles can individually or jointly affect the activity of supported heterogeneous catalysts. While the individual contribution of the supported metal to the overall activity of supported photocatalysts has been identified, the joint activity of mixed metal species is overlooked because of their different photoelectric properties. Here, atomically dispersed Pd (Pd₁) and Pd clusters are loaded onto CdS, serving as oxidation and reduction sites for methanol dehydrogenation. The Pd₁ substitutes Cd²⁺, forming hole-trapping states for methanol oxidation and assisting the dispersion of photodeposited Pd clusters. Therefore, methanol dehydrogenation on CdS with supported Pd₁ and Pd clusters exhibits the highest turnover frequency of 1.14 s^-1 based on the Pd content and affords H₂ and HCHO with a similar apparent quantum yield of 87 ± 1% at 452 nm under optimized reaction conditions. This work highlights the synergistic catalysis of supported metal for improved photocatalytic activity.